研究计划for,Joint,Program博士 博士拟研究计划

　 Research Plan for Joint Ph. D. Program

　Name

　Surname              First name 

　 Gender

　Date of birth (yy/mm/dd)

　College

　Major

　Domestic supervisor

　Hosting foreign country

　Hosting foreign institution

　Hosting faculty or department

　Hosting foreign supervisor

　Area of research

　Duration of study

　months (from  to  )

　RESEARCH PROJECT

　TITLE : Catalytic conversion of biomass to biochemicals

　BACKGROUND AND INTRODUCTION OF THE RESEARCH PROJECT:

　The 21st century is an era with a rapidly declining supply of petroleum and chemical resources. The economic growth around the globe is increasingly driving more need for energy and chemicals.《The Statistics of BP energy of the world》provides an authritive analysis of the situation of current resources in petroleum and chemicals. The petroleum reserves on the Earth can only sustain its production for about another 40 years; and those of coal and natural gas can sustain for another, respectively, 65 and 155 years. Currently, most countries in the world suffer from a shortage of energy resources. Renewable energy are especially attractive alternative. The utilization of fossil fuel results in green house effect and environmental pollution. Therefore, the exploitation of renewable energy in a large scale has already become a crucial part of energy strategies of every nation for future use. The conference of environment and development held in Rio de Janeiro in 1992 made the sustainable development one of agendas in the 21st century. To the question in Rio declaration, the US Chemical Industry made plans for from the time being to the year 2020. Reports about catalysis propose that renewable biochemical matters can be used as feeds, especially sugar, cellulose and other carbohydrates that can be used in the production of chemicals with high added value. Biochemical matters are abundant. For example, glucose, fructose, cellulose and etc, are renewable and, as feed, as carbon neutral in green house gas emission. They are potential alternative resources and are expected to play an important role in chemical production in the future.

　In recent years, investigation in this field has gradually become a hot topic in all major research institutions, but the need for new technologies and the cost of production are still unresolved for broad utilization of biochemical resources. Chemical processing can potentially address these issues. Biochemical raw materials undergo conversion by catalysis, which can decrease the cost of production and make the utilization of resources more energy efficient.

　REVIEW OF THE CURRENT RESEARCHES IN CHINA AND ABROAD:

　In China, in the field of catalytic transformations of biomass, KouYuan’s group of Beijing University is famous for their study on catalytic conversion of cellulose to C6-alcohol. Their work was published in J.A.C.S. in 2006[1]. Li Hexing’s group of Shanghai Normal University has also done some excellent researches on hydrogenation of glucose. They found a series of high activity amorphous alloy catalysts, and some papers have been published in the journals such as J. Catal, Appl.Catal, and Catal. Today [2,3,4].

　 At present, there are several research teams engage in the study on the catalytic conversion of biomass all over the world, of which, two research groups in this field have done outstanding work, including James A. Dumesic’s Group of American University of Wisconsin and Claude Moreau’s Group of the Organic catalysis and Catalytic materials Laboratory in Montpellier, France.

　 5-hydroxymethylfurfural (HMF) is an important biochemical and petrochemical intermediates. HMF and its

　 ensuing 2,5- disubstituted furan derivatives have great potential to be substitutes for the petrochemical materials. They can be used in the production of plastics, fine chemicals, antifungal agents, pharmaceuticals and even can be utilized to produce liquid alkanes and liquid fuels. The PNNL uses ionic liquids as a new type of sugar-soluble solvent to provide a new reaction system for the catalytic conversion of sugars. Through a series of tests on inorganic salts, they find an important catalyst (chromium(Ⅱ) chloride) that can catalyze the conversion of fructose and glucose to HMF with high yield. Through modification and modulation of the reaction phases, James A. Dumesic’s Group designed a biphase reaction system. Through the modulation ratio of DMSO, MIBK, PVP, and water, they obtain a high yield of HMF from fructose, glucose and even some polysaccharides such as sucrose and inulin. They are also trying to industrialize their product. Claude Moreau’s group, using different types of ionic liquids and cation exchange resin as catalysts, also find a high yield of HMF[9,10].

　 Some other labs also do their utmost to facilitate the utilization of biomass, for instance, Carlo Carlini’s group of Department of Chemistry and Industrial Chemistry in Italy. They have done researches on the dehydration of fructose over vanadium which has good activity [11].

　 CURRENT RESEARCH STAGE OF THE APPLICANT’S PROJECT IN CHINA:

　THE OBJECTIVES AND EXPECTED OUTCOMES OF THE PROJECT:

　Due to energy shortage, the development of new energy source has been one of the hottest research fields. The biomass-derived carbohydrates are abundant in China. However, little of them has been exploited. The objective of this study is to contribute to the development that besides the traditional use of combustion, renewable biomass resources will be also used in chemical engineering. It is very important to find high efficient catalytic systems and to convert carbohydrates and cellulose into high added value fine chemical products. In China, few researchers are working on this topic. We will explore new catalysts to promote biomass production.

　METHODOLOGIES :

　Firstly in the experiments, we need to synthesize some ionic liquids with special properties. The imidazolium ionic liquids are preferred so far. Compared with alkylamine or pyridine, they have lower melting point and viscosity, which can support mild reaction conditions. Because sugars could form hydrogen bonds with the organic nitrogen oxide group or electronegative anion, sugars can dissolve more easily. By using the solid carrier or heterogeneous catalyst (mineral salts or zeolites) in the ionic liquids, high-efficiency conversion can be realized.

　 Data will be collected and analyzed with HPLC. The NMR and MAS NMR are also needed for the structural analysis of the product and intermediate products, which may explain the mechanism of the reaction.

　THE BACKGROUND OF THE HOSTING FOREIGN INSTITUTE ON THIS PROJECT:

　THE TIMELINE OF THE PROJECT

　Sep.1, 2008-Dec.31, 2008

　 1. Synthesis and characterization of conventional 1-alkyl-3-alkylimidazolium halides ionic liquids. 

　 2. Synthesis and characterization of new designed ionic liquids with the organic nitrogen oxide functional group.

　3. Synthesis and characterization of nanosize and microsize particle zeolites.

　Jan.1, 2009-Apr.30, 2009

　1. Investigation on the production of HMF from fructose in conventional ionic liquids, the influence of different transition metal catalysts, and the characterization of the production.

　2. Investigation on the production of HMF from fructose in new designed ionic liquids, the influence of different transition metal catalysts and the characterization of the production.

　3. To modify the catalytic system and optimize of reaction conditions to improve the yield of object production.

　4. To support the proper metal on the zeolite and study the catalytic performance.

　5. To study the influence on the structure and mutarotation of fructose and the stability of the production over the optimalizing catalyst.

　May.1, 2009-Aug.31, 2009

　1. Investigation on the production of HMF from glucose in ionic liquids, the influence of different transition metal catalysts, and the characterization of the production.

　2. Investigation on the production of HMF from glucose in new designed ionic liquids, the influence of different transition metal catalysts and the characterization of the production.

　3. Discussion possible mechanism by the comparation with the reactions from fructose.

　4. To improve the purification processes of production.

　5. To study the recycle of the catalysts.

　THE STUDY/WORK PLAN AFTER RETURNING TO CHINA:

　 Continue to study on dehydration of fructose, glucose. Improve the yield of HMF by optimizing the reaction conditions.

　 Design new catalysts and study possible reaction mechanism through experiments and quantum chemical calculations.

　 Synthesize zeolites for the conversion of carbohydrates and characterize the three dimensional structure

　 of the zeolites.

　Study on the isomerization of glucose and fructose to find a suitable catalyst that makes it possible to converse glucose into high value-added fine chemicals through one-pot reaction .

　Study on the reactions of cellulose in ionic liquids to find a suitable catalyst for the conversion of cellulose.

　 REFERENCE:

　SIGNATURE OF CHINESE SUPERVISOR：

　                                           Date(yy/mm/dd):

　SIGNATURE OF HOSTING US SUPERVISOR:

　                                          Date(yy/mm/dd):

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